Herbicide

ABSTRACT

New and valuable herbicides based on mixtures of various herbicidal active ingredients.

United States Patent [1 1 [111 3,849,107 Fischer 1 Nov. 19, 1974 1 HERBICIDE [75] Inventor: Adolf Fischer, Mutterstadt, 1 References Cited Germany UNITED STATES PATENTS [73] Assignee: Badische Anilin- & Soda-Fabrik 3,257,190 6/1966 Soper 71/ 121 Akfiengesellschafi, 3,442,639 5/1969 Soper 71/121 LudWigShafen/Rhine Germany 3,449,111 6/1969 Wright 71/121 3,697,522 10/1972 Reicheneder et a1 71/92 X [22] Filed: July 13, 1971 21] App]. No; 162,317 Primary Examiner-James 0. Thomas, Jr.

Attorney, Agent, or FirmJ0hnst0n, Keil, Thompson & Sh t1 ff [30] Foreign Application Priority Data ur 6 July 28, 1970 Germany 2037265 [57] ABSTRACT [52] US. Cl 71/92, 71/87, 71/93, New and valuable herbicides based on mixtures of var- 71/1 11, 71/120, 71/121 ious herbicidal active ingredients. [51] Int. (11 A01n 9/22 1C! N D 58 Field of Search 71/92, 121 0 HERBICIDE The present invention relates to herbicides, particularly selective herbicides, which are suitable for controlling the growth of unwanted plants in crop plants.

It is known to use substituted dinitroaniline derivatives, phosphoric acids, pyridazones, substituted ureas, triazines and biscarbamates as herbicidal active ingredients. However, their action is not always satisfactory.

I have now found that herbicides comprising a mixture of a. a compound of the formula wherein R denotes hydrogen, nitro, alkyl, trifluoromethyl or methylsulfonyl, R denotes nitro, alkyl, triflu oromethyl or methylsulfonyl, R and R are identical or different and denote hydrogen, a linear or branched, saturated or unsaturated aliphatic radical which may be substituted by halogen, cyano, alkoxy or azido, or haloacetyloxyalkyl or alkylcarbamoyloxyalkyl, and R and R, together with the nitrogen atom whose substituents they are, may also form a hexamethylenimine ring, or

b. a compound of the formula where R denotes cycloalkyl or the radical 6 where X denotes alkoxy, thioalkyl, ammo, alkylamino, 5

dialkenylamino, alhaloalkylamino,

dialkylamino. kynylamino,

alkenylamino,

dialkynylamino,

acetylamino, haloacetylamino, dimethylformamidine, methylformamidine, acetoacetyl, the group N H-CO-COOR, -NH-CO-COSR, NH-COOR, -NH-COSR,

(300R coca cocn -NH-p0H -N\ I -N H J COOR COCH coca or -NH-CO-(CH -COOR,

R denoting substituted or unsubstituted alkyl, alkenyl, alkynyl, aralkyl, aryl, or cycloalkyl, or hydrogen, and the alkali metal, alkaline earth metal and substituted amine salts of these compounds, and n denoting one of the integers from 1 to 6, Y denotes chlorine, bromine, alkoxy or thioalkyl, and Z denotes haloalkyl, alkyl or hydrogen, or with d. a compound of the formula ca R-N where R denotes phenyl which may be substituted by halogen, nitro, alkyl, alkoxy, alkenoxy, alkynoxy, haloalkyl, alkyl or dialkylcarbamoyloxy, a cycloaliphatic, bicycloaliphatic or tricycloaliphatic radical which may be substituted by halogen or alkyl, 3-benzothiazolyl,

substituted or unsubstituted phenoxyalkyl, alkenyl or alkynylcarbamoyloxy, R denotes hydrogen, cyclooctenyl or cyclohexenyl, R denotes hydrogen, alkyl, alkoxy, alkoxyalkyl, isobuten-(1)-yl-3, a,a-dimethylpropargyl, cyanoalkyl, or carboxyalkyloxy, R further denotes an radical or its salts or esters, or with e. a compound of the formula JQLK,

RTHN N a where R denotes alkyl or cyanoalkyl, R denotes alkylamino, thioalkyl or azido, and X denotes halogen, alkoxy, thioalkyl or azido, or with f. a compound of the formula where R denotes phenyl which may be substituted by halogen, alkyl or haloalkyl, a linear or branched, saturated or unsaturated aliphatic radical which may be substituted by halogen, R further denotes alkoxyalkyl, alkyl or thioalkyl, Y denotes hydrogen or alkyl, R denotes alkyl or acetylalkyl, Z denotes oxygen or sulfur, and n denotes 1 or 0,

have a good herbicidal action, both preand postemergence, on weeds such as Chenopodium album, Galinsoga parviflora, Sinapis arvensis, Polygonum spp., Amaranthus spp., and Portulaca oleracea; on grassy weeds such as Poa spp., Bromus spp., Avena sativa and Cyperus spp.; and on millet types such as Panicum spp., Setaria spp., Digitaria spp., and Echinochloa spp. in the following crops: Gossypium spp., Soja hispida, Brassica napus, Beta spp., and Oryza sativa.

The individual active ingredients may be mixed to gether in any desired ratio; however, mixtures in which the ratio by weight of a or b to c, d, e orfis from 3:1 to 1:3 are preferred.

The phosphoric esters may be prepared by reacting salts of 0,0-diesters of thiophosphoric or dithiophosphoric acids with N-isobutynylchloroacetanilide. Preferred salts are alkali metal salts (Na,K) or R Nl-l salts, R denoting hydrogen, methyl, ethyl, isopropyl or npropyl. These salts may also be prepared during the reaction with the chloroacetamide from the acid concerned and the appropriate alkalis or amines. The reaction proceeds sufficiently quickly both in inert organic solvents such as ketones, ethers, aliphatic or aromatic hydrocarbons and in water or mixtures of water with one or more of the abovementioned organic solvents. The reaction temperature may be from room temperature to the boiling point of the solvent employed; however, the preferable range is from 40 to 120C.

EXAMPLE 1 Preparation of 0,0-diethyl-S-(N-isobutynyl-N- phenylcarbamoylmethyl)-dithiophosphoric acid 10.8 Parts by weight of the ammonium salt of 0,0-diethyldithiophosphoric acid and 11.1 pans of N- isobutynylchloroacetanilide are dissolved in a mixture of 50 parts of acetone and 10 parts of water. The mixture is heated for 4 hours at 60C and diluted, after cooling, with water, and the product is dissolved in toluene or methylene chloride. The organic phase is washed once with a 5% by weight aqueous sodium carbonate solution and several times with water. After drying over sodium sulfate, the solution is concentrated in vacuo, finally under an oil pump vacuum, at less than 70C. There is obtained 16.3 parts of the above compound as a pale yellow oil. n 1.5540.

phenylcarbamoylmethyl)-thiophosphoric acid Adopting the procedure of Example 1, 15.1 parts of the above compound (n 1.5273) was obtained from 9.9 parts of the ammonium salt of 0,0-diethylthiophosphoric acid and l 1.1 parts of N- isobutynylchloroacetanilide.

calc.: 3. found: 3

The agents according to the invention may be used as solvents, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than C, e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and having one or more than one functional group, e.g. the keto group, the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g. polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be pre pared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g. kieselguhr,

talc, clay or fertilizers.

To improve the action, wetting agents and adhering agents or oils may also be added.

EXAMPLE 3 An agricultural plot was sown with Gossypium hirsutum, Setaria viridis, Echinochloa crus-galli, Bromus tectorum, Amaranthus retroflexus and Portulaca oleracea and subsequently treated with the following amounts of the following individual active ingredients and mixtures of them, each active ingredient and each mixture being emulsified or dispersed in 500 liters of water per hectare:

I N-allyl-N-B-chloroethyl-2,6-dinitro-4- trifluoromethylaniline, 1.5 and 4 kg per hectare;

N-propyl-N-B-chloroethyl-2,6-dinitro-4- trifluoromethylaniline, 1 and 4 kg per hectare; lll N-propylN-B-cyanoethyl-2,6-dinitro-4- trifluoromethylaniline, 2 and 4 kg per hectare; IV N-ethyl-N-B-chloroethyl-Z,6-dinitro-4- trifluoromethylaniline, 2 and 3 kg per hectare; V N,N-dipropyl-2,6-dinitro-4-methylsulfonylaniline,

1.5 and 3 kg per hectare;

V1 N-m-trifluoromethylphenyl-N- l -cyclohex- 1 -enyl- N',N'-dimethylurea, 2.5 and 4 kg per hectare; V11 N-m-chlorophenyl-N-l-cyclohex-1-enyl-N',N-

dimethylurea, 3 and 4 kg per hectare;

Vlll N-p-fluorophenyl-N- 1 -eyclohex- 1 -enyl-N- methylurea, 2 and 4 kg per hectare; 1X N-m-trifluoromethylphenyl-N,N-dimethylurea,

1.5 and 3 kg per hectare;

X N-p-chlorophenyl-N,N'-dimethylurea, 1 and 3 kg per hectare;

1+ .\/1 1.5 2.5 kg per hectare;

N-3-chlorophenyl-N-cyclohexl -enyl-N methylurea; N-3-chloro-4-methoxyphenyl-N-cyclohexl -enyl-N methylurea; N-4-chlorophenyl-N'cyclohexl -enyl-N methylurea; N-phenyl-N-cyclohex-I-enyl-N-methylurea; N-phenyl-N-cyclohexl -enyI-N 'N-dimethylurea; 1-( m-tert-butylcarbamoyloxyphenyl )-3-methylurea; l-( m-ethylcarbamoyloxyphenyl)-3-methylurea; l-( m-allyl-tert-butylcarbamoyloxyphenyl )-3 ,3-

dimethylurea; I-(m-a,a-dimethylpropyn-( l )-yl- (3 )carbamoyloxyphenyl)-3-methyl-3- methoxyurea; l-(m-ot-methyl-a-ethylpropyn-( l )-yl- (3 )carbamoyloxyphenyl )-3-methyl-3" methoxyurea; 1-( m-tertbutylallylcarbamoyloxyphenyl )-3-methyl- 3-methoxyurea; N-m-trifluoromethylphenyl-N-butyn-( l )-yl-( 3 urea; N-3-chloro-4-methoxyphenyl-N-methyl-N- methoxyurea; N-m-trifluoromethylphenyl-N-methoxymethyl-N- methylurea;

I N-m-trifluoromethylphenyl-N-methoxymethyl-N'- methyl-N"methxyurea; N-m-trifluoromethylphenyl-N-acetyloxymethyl- N,N-dimethylurea; N-4-br0mophenyl-N-cycl0hexl -enyl-NN- dimethylurea; N-3 ,4-dichlorophenyl-N-cyclohexl -enyl-NN- dimethylurea;

EXAMPLE 4 In a greenhouse, loamy sandy soil was filled into pots and sown with Gossypium hirsutum, Digitaria sanguinalis, Echinochloa crus-galli, Amaranthus retroflexus and Portulaca oleracea. The soil prepared in this manner was subsequently treated with the following amounts of the following individual active ingredients and mixtures of them, each active ingredient and each mixture being dispersed of emulsified in 500 liters of water per hectare;

I N-alkyl-N-B-chloroethyl-2,6-dinitro-4- trifluoromethylaniline, 2 and 4 kg per hectare;

N-propyl-N-B-chloroethyl-2,6-dinitro-4- trifluoromethylaniline, l and 3 kg per hectare;

III N,N-dipropyl-2,6-dinitro-4- trifluoromethylaniline, 1.5 and 3 kg per hectare; IV 2-chloro-4-ethylamino-6-butyn- 1 -yl-3-amino- 1,3,5-triazine, 2 and 3 kg per hectare; V 2-chloro-4-ethylamino--methoxyisopropylamino- 1,3,5-triazine, 1.5 and 3 kg per hectare; VI 2-thiomethyl-4,6-diisopropylamino-l ,3,5-triazine,

2 and 4 kg per hectare;

I VI 2 2 kg per hectare;

II IV 1 2 kg per hectare;

III V: 1.5 1.5 kg per hectare.

After 4 to 5 weeks it was ascertained that the mixtures had a stronger herbicidal action than the individual active ingredients, combined with more favorable crop plant compatibility.

The results of the experiment are given in the following table.

Table I I III IV V VI I+VI II+IV lIl+V kg/ha 2 4 I 3 L5 3 2 3 1.5 3 2 4 2+2 1+2 l.5+l.5

Gossypium 0 l5 0 20 0 20 5 l5 5 25 0 20 0 O 0 hirsutum Digilariu 80 I00 85 I00 80 I00 65 85 75 80 85 I00 I00 I00 sunguinalis Echinochlou 85 I00 85 I00 85 I00 60 90 45 80 90 I00 I00 I00 crus-gulli Amurunthus 25 80 25 70 20 )0 I00 70' I00 I00 I ()0 I 00 retroi'lexus Portulaca 30 25 70 25 55 60 I00 70 I00 60 I00 I00 I00 I00 oleruccu 0 no dnmngc I00 complete destruction N-3-chloro-4-methoxyphenyl-N-cyclohexl -enyl- NN-dimethylurea;

N-[lor 2-(3a, 4, 5, 6,7,7a-hexahydro)-4- methanoindanyl]-NN-dimethyl-N-cyclohexl enylurea;

N-m-trifluoromethylphenyl-N-cyclooct-1-enyl-NN- dimethylurea;

N-m-trifluoromethylphenyI-N-cyclooctyll -enyl-N'- methylurea;

N- 5-( 3a,4,5,6,7,7a-hexahydro-4-methanoindanyl -NN'-dimethylurea; N- lor 2-( 3a,4,5,6,7,7a-hexahydro)-4- methanoindanyl -N'N-dimethylurea; N-bicycIo-( 3,3,0)-octyl-NN-dimethylurea; N-3,4-dichlorophenyl-N'N-dimethylurea; N-cyclooctyl-N'N'-dimethylurea; or N-m-dimethylcarbamoyloxyphenyl-N-methylurea.

The action of the following mixtures corresponds to that of those above:

N,N-dipropyl-2,6-dinitro-4-methylsulfonylaniline;

N-ethyl-N-butyl-2,6-dinitro-4-methylsulfonylaniline;

55 N-B-methoxyethyl-N-B-chloroethyl-2,6-dinitro-4- N-propyl-N-B-bromoethyl-2,6-dinitr-4- trifluoromethylaniline; N,N-bisB-( chloroethyl )-2,6-dinitro-4- trifluoromethylaniline;

N,N-bis-B-(chloroethyl)-2,6-dinitr0-4-methylaniline; 2O

N-propyl-N-allyl-4,6-dinitro-2- trifluoromethylaniline; N-ethyl-N-,B-azidoethyl-2,6-dinitro-4- trifluoromethylaniline; N-propyl-N-B-azidoethyl-2,6-dinitro-4- trifluoromethylaniline; N-propyl-N-B(chloroacetyloxy)-ethyl-2,6-dinitro-4- trifluoromethylaniline; N,N-bis-(B-chloroacetyloxy)-ethy1-2,6-dinitro-4- trifluoromethylaniline; N-(B-chloroacetyloxy)-ethyl-2,6-dinitro-4- trifluoromethylaniline; y N-(B-methylcarbamoyloxy)-ethyl-2,6-dinitro-4- trifluroromethylaniline; bromoethyl-2,6-dinitro-4-trifluromethylaniline; N-B-methoxyethyl-N-B-bromoethyl-2,6-dinitro-4- trifluoromethylaniline; N-y-chloropropyl-N-flahloroethyl-2,6-dinitro-4- trifluoromethylaniline; N-propen-( 1 )-yl-( 3 )-N-B-chloroethyl-2,6-dinitro-4- methylaniline; N-propyl-N-,B-chl0r0ethyl-2,6-dinitro-4- methylaniline; N-propyl-N-B-azid0ethyl-2,6-dinitro-4- methylaniline; N-propyl-N-,8-azidoethyl-2,6-dinitro-4- methylsulfonylaniline; N-propyl-N-,8-bromoethyl-2,6-dinitro-4- methylsulfonylaniline;

N-pr0pyl-N-B-(chloroacetyloxy)-ethyl-2,6-dinitro-4- 50 methylaniline; N-propyl-N-B-( chloroacetyloxy )-propyl-2 ,6-dinitro- 4-trifluoromethylaniline; or N-pr0pyl-N-/3-(methylcarbamoyloxy)-propyl-2,6-

W 2-chlore-4-ethylamino-6-a,a-dimethylpropargylamino-l ,3,5-triazine; 2-chl0ro-4-isopropylamino-6-a,a-dimethylpr0pargylamino- 1 ,3,5-triazine;

5 2-thiomethyl-4-ethylamino-6-butynl -yl-3amino- 1,3,5-triazine; 2'chloro-4-ethylamino-6-sec-bu'tylaminol 35- triazine; 2-chloro-4-ethylamino-6-a,a-dimethylcyanomcthylaminol ,3,5-triazine;

2-chloro-4-isopropylamino-6-diethylaminn- 1.3.5-

triazine; 2-methoxy-4-isopropylamino-6-ethylaminol 3,5-

triazine; l5 2-thiomethyl-4-isopropylamino-b-tert-butylamino- N-methyl-N-B- 1,3,5-triazine; or 2-azido-4-sec-butylamino-6-thi0mcthyl- 1 ,3 ,5-

triazine.

EXAMPLE 5 An agricultural area was sown with Soja hispicla, Digitaria sanguinalis, Bromus tectorum, Amaranthus retroflexus and Portulaca oleracea and subsequently treated with the following amounts of the following individual active ingredients and mixtures of them, each active ingredient and each mixture being dispersed or emulsified in 500 liters of water per hectare:

I N-allyl-N-B-chloroethyl-2,6-dinitro-4- trifluoromethylaniline, l and 3 kg per hectare;

N-propyl-N-B-chloroethyl-2,6dinitro-4- trifluoromethylaniline, l and 2 kg per hectare; III I N, N-dipropyl-2,6-dinitro-4 trifluoromethylaniline, 1 and 3 kg per hectare; IV l-m-trifluor0methylphenyl-4-dimethylamin0-5- chloropyridazone-6, 2 and 3 kg per hectare; V l-phenyl-4,5-dimethoxypyridazone-6, l and 2 kg per hectare; VI 1-m-methylphenyl-4-methoxy-S- bromopyridazone-6, 2 and 3 kg per hectare; VII N-m-trifluoromethylphenyl-N-cyclohexl -eny1- N',N-dimethylurea, 2 and 3 kg per hectare;

VIII N,N-dimethyl-N-[N"-methoxyisopropylcarbamoyloxyphenyH-urea, l and 2 kg per hectare; IX N-4-(p-chlorophenoxy)-phenylN,N-

dimethylurea, 2 and 3 kg per hectare;

2'chl0ro-4-ethylamino-6-(a,a-

dimethylcyanomethyl)-amino- 1,3,5-triazine, I and 2 kg per hectare;

I IV l 2 kg per hectare;

II V 1 1 kg per hectare;

Ill 3 VI: 1 2 kg per hectare;

I VII 1 2 kg per hectare;

II +VIII 1 1 kg per hectare;

III IX l 2 kg per hectare;

I+ X: 1 +1 kg per hectare.

.55 dlmtro'4'mfluoromethylamlme After 4 to 5 weeks it was ascertamed that the mixwith tures had a stronger herbicidal action than the individ- 2-chlor0-4-ethylamino-6-butyn-l-yl-3-amino-1,3,5- ual active ingredients, combined with more favorable triazine; crop plant compatibility. 2-chl0r0-4-ethylamino-6-methoxyisopropylamino- The results of the experiment are given in the followl,3,5-triazine; ing table:

TABLE 1 I1 111 1v v VI VII VIII IX X mum 1 3 1 2 1 3 2 a 1 2 2 3 2 a 1 2 2 a 1 2 Qua 1111 m. 0 l5 0 m 0 2o 0 m 0 no 0 111 0 2o 0 20 5 25 u 20 [Hr Harm xum nh/ullamm" 101) N5 100 7!] NH) (I5 I15 55 Ill) 50 I00 45 35 (ll) .10 30 75 llrmmuvHolmium... 70 llll) 71') Hill 70 I00 55 Ill] 55 U5 -lll (l5 [Ill 75 50 95 55 R0 50 J5 Amarantlum rvlroflnruun. 15 no J5 50 I5 50 00 245 70 100 71] U5 U0 100 50 115 45 1m 45 Iorlulacaolrmcm .2 15 55 (I0 85 70 U5 (l5 U0 05 100 (10 J5 T0 100 1'( m-allyl-tert-butylcarbamoyloxyphenyl)-3,3-

dimethylurea;

l-( m-a,a-dimethylpropyn-( l )-yl- (3 )carbamoyloxyphenyl)-3-methyl-3- methoxyurea;

l-(m-a-methyl-a-ethylpropyn( l )-yl- (3 )carbamoyloxyphenyl )-3methyl-3- methoxyurea;

1-( m-tertbutylallylcarbamoyloxyphenyl )-3 methyl- 3-methoxyurea;

N-3-chloro-4-methoxyphenyl-N -methyl-N methoxyurea;

N-m-trifluoromethylphenyl-N-methoxymethyl-N- methylurea;

N-m-trifluoromethylphenyl-N-methoxymethyl-N'- methyl-N'-methoxyurea;

N-m-trifluoromethylphenyl-N-acetyloxymethyl- N,N dimethylurea;

N-m-trifluoromethylphenyl-N-cyclohexl -enyl-N- methylurea;

N-3-chl0rophenyl-N-cyclohexl -enyl-N'- methylurea;

EXAMPLE 6 An agricultural plot was sown with Gossypium hirsutum, Soja hispida, Digitaria sanguinalis, Bromus tectorum, Amaranthum retroflexus and Polygonum persicaria, and subsequently treated with the following teclnrum N-3-chl0ro-4-methoxyphenyl-N-cyclohex-l-enylN- 25 amounts of the following individual active ingredients methylurea; and mixtures of them, each active ingredient and each N-4-chlorophenyl-N-cyclohex-1-enyl-N'- mixture being emulsified or dispersed in 500 liters of methylurea; water per hectare: N-phenyl-N-cyclohexl -enyl-N-methylurea; I 0,0-diethyl-S-[N-phenyl-N-butynl -yl-( 3 N-phenyl-N-cyclohex-l-enyl-N'N'-dimethylurea; 3O carbamoylmethyll-dithiophosphoric acid, 1, 2 and N-4-bromophenyl-N-cyclohex-l-enyl-NN'- 3 kg per hectare;

dimethylurea; II 0,0-diethyl-S-( N-butyn- 1 -yl-( 3 )-N- N-3,4-dichlorophenyl-N-cyclohexl -enyl-NN- phenylcarbamoylmethyl)-thiophosphoric acid, 1 2

dimethylurea; and 3 kg per hectare; N-3-chl0ro-4-meth0xyphenyl-N-cyclohexl-enyl- 3 5 III 1-( 3-trifluoromethyl)-phenyl-4-methoxy-5- NN-dimethylurea; chloropyridazone-6, 2 and 3 kg per hectare; N-[lor 2- (3a,4,5,6,7,7a-hexahydro-4)- IV 1-phenyl-4,5-dimeth0xypyri.dazone-6, l and 2 kg methanoindanyl]-NN-dimethyl-N cyclohex-lper hectare; enylurea; V N-m-trifluoromethylphenyl-N- l -cyclhexl -enyl- N-m-trifluoromethylphenyl-N-cyclooct-1-enyl-N'N'- 40 N-dimethylurea, 2 and 3 kg per hectare;

dimethylurea; VI N-m-trifluoromethylphenyl-N,N-dimethylurea, N-m-trifluoromethylphenyl-N-cyclooctyl-l-enyl-N- 2 and 3 kg per hectare;

methylurea; VII 2-chloro-4-ethylamino-6-methoxyisopropyl- N-[-(3a,4,5,6,7,7a-hexahydro-4)-methanoindanyl]- 1,3,5-triazine, 1 and 3 kg per hectare;

N'N'-dimethylurea; 45 I III l 2 kg per hectare; N-[ 1- or 2-(3a,4,5,6,7,7a-hexahydro-4-)methanoin- II IV l 1 kg per hectare; danyl]-N'N-dimethylurea; I V l 2 kg per hectare; N-bicyclo-(3,3,0)-octyl-N'N-dimethylurea; II VI l 2 kg per hectare; N-3,4-dichlorophenyl-NN-dimethylurea; I VII 2 1 kg per hectare. N-cyclooctyl-N'N-dimethylurea; 50 After 4 to 5 weeks it was ascertained that the mix- N-m-dimethylcarbamoyloxyphenyl-N-methylurea; tures had a better herbicidal action than the individual N-p-chlorophenyl-N-l -cyclohexl -enyl-NN'- active ingredients, combined with more favorable crop dimethylurea; plant compatibility. N-p-fluorophenyl-N-l-cycl0hexl -enyl-N- 5 5 The results of the experiment are given in the followmethylurea; ing table:

Table l n m IV v VI VII kg/ha 2 3 l 2 3 2 3 1 2 2 3 2 3 1 3 Gussypium o 0 2o 0 I0 25 0 l5 0 IS 0 0 1o 0 hirsutum Suju hispidu o 0 l() o lo 20 10 0 o 0 20 I0 20 0 Digiurriai ao I00 I00 so I00 100 65 95 90 70 I00 9o 100 B25332 so I00 I00 so m0 100 so 4s as too so so 10 Table Continued 1 11 111 1V V V1 V11 kg/hu 1 2 3 l 2 3 2 3 1 2 2 3 2 3 l 3 Amarunlhus 3O 55 9U 20 4(1 65 65 95 75 101) 70 100 75 100 95 100 relroflcxus Polygonum 1O 2O 30 1O 15 25 70 100 80 100 80 100 75 100 70 100 persicaria 1+111 11+1V 1+V |1+V1 1+V11 kg/ha 1+2 1+1 1+2 1+2 2+1 Gossypium hirsutum 0 O 0 Soja hispicla 0 0 10 (1 Digitaria sanguinalis 100 100 100 100 100 Bromus tectorum 100 100 100 100 100 Amaranthus retroflexus 100 100 100 100 100 Polygonum persicaria 9O 95 100 95 l()() O no damage 100 complete destruction EXAMPLE 7 EXAMPLE 8 In a greenhouse, the plants Gossypium hirsutum, Soja torum, Amaranthus retroflexus and Polygonum persicaria were treated at a growth height of 3 to cm with the following amounts of the following individual active ingredients and mixtures of them, each active ingrediem and each mixture being emulsified or dispersed in 500 liters of water per hectare:

I 0,0-dimethyl-S-(N-butyn-1-y1-(3)-N- phenylcarbamoylmethyl)-dithiophosphoric acid, 1 and 4 kg per hectare;

11 0,0-dimethyl-S-( N-butyn- 1 -yl-( 3 )-N- phenylcarbamoylmethyl)-thiophosphoric acid, 1.5

and 3 kg per hectare;

111 1-m-trifluoromethylphehyl-4-dimethylamino-5- chloropyridazone-6, 3 and 4 kg per hectare;

1V N-m-trifluoromethylphenyl-N- l -cyclohex- 1 -enyl- N,N'-dimethylurea, 1.5 and 3 kg per hectare; 1+ 111 1 1 kg per hectare;

11 IV 1.5 1.5 kg per hectare.

The spray liquids were sprayed onto the undersides of the leaves. After 3 to 4 weeks, it was ascertained that the mixtures had a stronger herbicidal action than the individual active ingredients, combined with superior crop plant compatibility.

The results of the experiment are given in the follow- In a greenhouse, loamy sandy soil was filled into pots 5 and sown with Brassica napus, Beta vulgaris, Echinochloa crus-galli, Avena fatua, Sinapis arvensis and Galinsoga parviflora; subsequently, the soil prepared in this manner was treated with the following amounts of the following individual active ingredients and mixtures of them, each active ingredient and each mixture being dispersed or emulsified in 500 liters of water per hectare:

I 0,0-diethyl-S- N-phenyl-N-butynl -yl-( 3 carbamoylmethyl]-dithiophosphoric acid, 1.5 and 3 kg per hectare;

11 0,0-diethyl-S-(N-isobutynyl-N- phenylcarbamoylmethyl)-thiophosphoric acid, 1

and 4 kg per hectare;

111 dimethylaminoethanol salt of N-[ l-phenyl-S- bromopyridazon-6-yl-(4)l-oxamic acid, 1.5 and 3 kg per hectare;

1V 1-phenyl-4-amino-5-chloropyridazone-(6), 3 and 4 kg per hectare; 1+ 111 1.5 1.5 kg per hectare;

I1+1V l -l 3 kg per hectare.

After 4 to 5 weeks, it was ascertained that the mixtures had a stronger herbicidal action than the individual active ingredients, combined with superior crop i bl plant compatibility.

Table 1 11 111 IV 1+111 11+1V kg/ha l 4 1.5 3 3 4 1.5 3 1 +1 1.5 +1.5

Gossypium hirsutum 0 25 0 20 0 10 O 20 0 O Soja hispida 0 25 0 20 10 25 0 25 10 O Zezrmays 0 20 0 20 1O 25 (1 15 10 0 Echmochlou Crus-galli 80 100 95 100 70 100 100 100 100 Bromus tectorum 80 100 80 100 70 100 100 100 100 Amarunthus retroflexus 40 100 40 80 95 60 100 100 100 Polygonum persicaria 20 25 80 70 100 100 100 U no damage 100 complete destruction The results of the experiment are given in the following table:

0,0'dimethyl-S-( N-butynl -yI-( 3 )-N phenylcarbamoylmethyl)-dithiophsphoric acid;

Table I II III IV I. III II IV kg/ha l 3 I 4 l.5 5 1 4 IS+I.5 I+3 Brassica napus 0 I0 0 0 IS I5 0 I5 Bela vulgaris 0 20 0 0 I5 0 I0 0 0 Echinochloa crus-gulli 80 I00 95 I00 75 I00 65 75 I00 I00 Avena fuluu 60 I00 65 I00 70 75 I00 I00 Sinapis arvensis l() 20 I0 30 80 I00 80 I00 95 I00 Galinsoga parviflora I0 20 I0 20 65 I00 70 85 80 X0 0 no damage I00 complete destruction EXAMPLE 9 l5 methyl-O-methyl-S-(Nbutyn-l-yl-(3)-N- I In a greenhouse the plants Beta vulgaris, Oryza sativa, Echinochloa crus-galli, Avena fatua, Galinsoga parviflora and Chenopodium album were treated at a growth height of 2 to 12 cm with the following amounts of the following individual active ingredients and mixtures of them, each active ingredient and each mixture being dispersed or emulsified in 500 liters of water per hectare:

I 0,0-dimethyl-S-(N-butyn-l-yl-(3)-N- phenylcarbamoylmethyl)-dithiophosphoric acid, 0.5, l and 2 kg per hectare;

0,0-dimethyl-S-(N-butyn-l-yl-(3)-N- phenylcarbamoylmethyl)-thiophosphoric acid, I, 1.5 and 3 kg per hectare;

III dimethylaminoethanol salt of N-[ l-phenyl-S- bromopyridazon-6-yl-(4)]-oxamic acid, 1.5, 2 and 3 kg per hectare;

IV 3-methoxycarbonylaminophenyl-N-(3'-methyl phenyl)-carbamate, 0.5, l, 1.5 and 2 kg per hectare;

I III 0.5 l.5 kg per hectare; I I- IV 1 1 kg per hectare;

II III I 2 kg per hectare;

II IV l 0.5 kg per hectare.

After 3 to 4 weeks it was ascertained that the mixtures had a stronger herbicidal action than the individual active ingredients, combined with superior crop plant compatibility.

phenylcarbamoylmethyl)-dithiophosphoric acid; ethyl-O-ethyI-S-(N-butyn- 1 -yl( 3 )-N- phenylcarbamoylmethyl)-dithiophosphoric acid; 0,0-diallyl-S-(N-butynl -yl-( 3 )-N- phenylcarbamoylmethyl )-dithiophosphoric acid; ethyl-O-methyI-S-( N-butyn- I -yl-( 3 )-N- phenylcarbamoylmethyl)-dithiophosphoric acid; phenyl-O-ethyl-S-(N-butyn- I -yI-(3 )-N- phenylcarbamoylmethyl)-dithiophosphoric acid; 0,0-diphenyl-S-(N-butyn-1-yl-(3)-N- phenylcarbamoylmethyl)-dithiophosphoric acid; 0,0-diethyl-S-( 3 ,S-dimethylmorpholine-N- carbamoylmethyl)-dithiophos'phoric acid; 0,0-diethyl-S-(2,5-dimethyImorphoIine-N- carbamoylmethyl )-dithiophosphoric acid; 0,0-diethyl-S-( N-ethyl-N-B methylphenylcarbamoylmethyl )-dithiophosphoric acid; 0,0-diethyl-S-(N-isopropyl-N-3- phenylcarbamoylmethyl )-dithiophosphoric acid; 0,0-diethyl-S-(N-propargyI-N- phenylcarbamoylmethyl)-dithiophosphoric acid; 0,0diethyl-S-(N-bromobutynl -yl-( 3 )-N- phenylcarbamoylmethyl)-dithiophosphoric 0,0-diethyI-S-(N-cyanomethyI-N- phenylcarbamoylmethyl )-dithiophosphoric acid; 0,0-diethyl-S-( N-ethyI-N-phenylcarbamoylmethyl dithiophosphoric acid;

acid;

The results of the experiment are given in the follow 0,0-diethyI-S-(N-methyI-N- ing table: phenylcarbamoylmethyl)-dithiophosphoric acid;

Table i I II III IV kg/ha 0 5 I 2 l 1.5 3 1.5 2 3 0.5 I L5 2 Beta vulgaris 0 t 0 2O 0 5 30 0 0 I5 0 0 I5 20 Oryga sativa 0 O 20 0 5 25 0 I0 20 0 0 2O 30 Echlnochloa CHIS-gall! 80 I00 90 95 I00 95 I0 20 3O 40 Avena fatua 70 I00 I00 I00 I00 40 55 80 IO 20 25 30 Galinsoga parviflora I0 20 35 15 2O 40 70 55 I00 80 I00 '100 Chenopodium album 10 20 35 I5 25 45 80 I00 I00 85 I00 I00 I+III I+IV II+III II+IV kg/ha 0.5+l.5 I +l 1+2 l+0.5

Beta vulgaris 0 0 0 0 Oryza sativa 0 0 I0 0 Echinochloa crus galli I00 I00 I00 Avena fatua I00 I00 I00 95 Galinsoga parviflora 90 I00 I00 95 Chenopodium album I00 I00 I00 I00 0 no tliummc I00 culuplulc \ICNII'IIUIlIHI The action of the following mixtures corresponds to that of the mixtures in Examples 4 and 5:

0,0-diethylS-( N-butynl -yI-( 3 )-N- phenylcarbamoylmethyl)-dithiophosphoric acid;

0,0-diethyl-S-( N-pentyn- I -yI-( 3 )-N- phenylcarbamoylmethyl )-dithiophosphoric acid;

0,0-di-(isopropyl )-S-(N-butyn-( l )-yl-( 3 )-N- phenylcarbamoylmethyl )-dithiophosphoric acid;

l-m-trifluoromethylphenyl4-dimethylamino-5- chloropyridazone-6, 2.5 and 4 kg per hectare; I X 1.5 2.5 kg per hectare; II VI l 2 kg per hectare; III Vll 2 2 kg per hectare; 5 IV VIII 3 1 kg per hectare; V IX l 3 kg per hectare.

After 4 to 5 weeks it was ascertained that the mixtures had a stronger herbicidal action than the individtrifluoromethylaniline, 2 and 3 kg per hectare;

IV dimethylaminoethanol salt of N-[ l-phenyl-S- bromopyridazon-6-yl-(4)]-oxa'mic acid. L5 and 3 kg per hectare;

V l-phenyl-4-amino-5-chloropyridazone-6. 3 and 4 kg per hectare;

VI 3-methoxycarbonylaminophenyl-N-( 3 -methylphenyl)-carbamate, I and 2 kg per hectare;

ual active ingredients, combined with superior crop 1%; kg i F plant compatibility. HI Vi 2 i per ectare' The results of the experiment are given in the follow- I per hectare ing table: After 2 to 3 weeks it was ascertained that the mix- TABLE I II III Iv v VI VII VIII IX X KgJha 4 1 3 2 4 3 4 1 4 2 a 2 4 1 4 a 4 2.5 4 (ra alm hzrsutum 0 2o 0 0 25 0 o o 25 0 15 0 25 0 45 0 5 o 25 Selariafaberii 55 100 50 100 55 100 55 100 55 100 45 75 55 so 45 too so 45 75 Amaranthuaretroflexus 25 75 25 75 15 25 3o 15 5o 55 so 75 55 55 100 50 so 50 so Portulaca oleracea... so so 25 70 3o 55 25 55 2o 55 so so 55 55 100 55 so 55 95 Cyporusesculemus I5 2o 2o 45 20 3o 20 50 so 40 75 55 100 40 55 45 so I+X II+vI III+vII IV+VIII V+IX KgJha 1 5+2.5 1+2 2+2 3+1 1+5 Gossypium hirsutum 0 0 0 0 0 Setaria faberii 100 100 100 100 100 Amaranthus retroflexus 100 100 85 95 100 Portulaca oleracea 100 100 95 100 100 Cyperuo esculentus 100 80 90 80 N0TE.O=I10 damage; 100=complete destruction.

EXAMPLE 1 l The following amounts of the following individual ac- 3 5 tive ingredients and mixtures of them were each emulsifted or dispersed in 500 liters of water per hectare and sprayed onto plants (growth height: 7 to 12 cm) of Beta tures had a far stronger herbicidal action than the individual active ingredients, combined] with superior compatibility with Beta vulgaris.

The results of the experiment are given in the following table:

Table I II III IV V VI l+lV ll-l-V lll+Vl kg/ha 1.5 3 l 4 2 3 1.5 3 3 4 l 2 1.5-+1.5 l+3 2+] Beta vulgaris 0 35 0 35 0 5 0 l5 0 IO 0 20 0 0 0 Setaria faberii 45 5O 40 8O 35 70 30 6O 20 40 100 100 90 Bromus tectorum 40 80 45 9O 4O 80 35 7O 35 70 I5 30 100 I00 85 Galinsoga parviflora I0 30 10 25 I0 20 35 9O 45 8O 50 [0O 85 85 85 Sinapis arvensis I5 35 15 35 10 30 55 90 45 65 90 90 I00 0 no damage I00 complete destruction vulgaris, Setaria faberii, Bromus tectorum, Galinsoga I claim:

I. A process for controlling the growth of unwanted plants which comprises applying a phytotoxic amount of a mixture of (a) N-propyl-N- -chloroethyl-2,6- dinitro-4-trifluoromethylaniline and (b) l-phenyl-4 amino-5-chloropyridazone-(6), the weight ratio of azb being in the range of 1:3 to 3zl.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3 3,849,107

6 DATED November 19, I974 |NVENTOR(S) Adolf Fischer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: I 0 In Column 9, Line 34, delete "methyl" and substitute-ethyl-- In Column 10, Line 51, delete "III 3VI:"- and substitute -III VI:- g

In Column 10, Line 55, delete "I+X" and substitute -II X- In Column 20, Line 39, delete "ethyl" and substitute --enyl- In Column 21, Line 37, delete "butyl" and substitute --butyn-- In Column 22, Line 1, delete "butyl" and substitute --butyn- In Column 22, Line 18, delete "butyl" and substitute-butyn-- In Column 22, Line 31, delete "butyl" and substitutebutyn- In Column 26, Line 9, delete "1,5" and substitute --l.5--

Q Signed and Scaled this Third Day oF'A 1976 [SEAL] Arrest:

RUTH C. MACON C. MARSHALL DANN Arresting Offrcer Commissioner ofPatents and Trademarks 

1. A PROCESS FOR CONTROLLING THE GROWTH OF UHNWANTED PLANTS WHICH COMPRISES APPLYING A PHYTOXIC AMOUNT OF A MIXTURE OF (A) N-PROPYL-N- -CHLOROETHYL-2,6-DINITRO-4TRIFLUOROMETHYLANILINE AND (B) 1-PHENYL-4-AMINO-5CHLOROPYRIDAZONE-(6), THE WEIGHT RATIO OF A:B BEING IN THE RANGE OF 1:3 TO 3:1. 